Production of monomethyl diallyl isocyanaurate



3,522,253. Patented July 28, 1970 r 3,522,253 PRODUCTION OF MONOMETHY L DIALLYL ISOCYANAURATE v I Edwin D. Little, Jr., and Charles R. Walter, Jr., Hopewell, Va., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Oct. 23, 1965, Ser. No. 504,157 Int. Cl. C07d 55/38 US. Cl. 260-248 3 Claims ABSTRACT OF THE DISCLOSURE Monomethyl diallyl isocyanurate is produced by a process which comprises reacting diallyl isocyanurate with dimethyl sulfate; The subject compound has been found to be useful as a monomer in the production of resinous polymers and copolymers.

This invention relates to a novel compound, monomethyl diallyl isocyanurate, and the preparation thereof from diallyl isocyanurate.

It is known that amines are readily methylated by dimethyl sulfate, however, it has hitherto not been thought possible to methylate diallyl isocyanurate. Indeed, cyanuric acid resists methylation by dimethyl sulfate.

It is therefore an object of this invention to provide a process whereby a novel compound, monomethyl diallyl isocyanurate will be produced.

This and other objects will flow from and become apparent from the following description of the invention.

In accordance with the present invention, it has now been discovered that monomethyl diallyl isocyanurate is produced by.a process which comprises reacting diallyl isocyanurate with dimethyl sulfate as illustrated by the following reaction:

The subject compound has been found to be useful as a monomer convertible into resinous polymers and copolymers having high resistance to chemical action and in addition properties superior to polymers made from known triallyl isocyanurate.

While the proportions of the reactants may range from equimolar amounts all the way to an excess of methyl sulfate (about 100% by weight excess) it has been found preferable to use equimolar amounts of diallyl isocyanurate and dimethyl sulfate.

The reaction is carried out at a temperature between about 20 and about C., preferably about 25 C., in aqueous solution containing, preferably, at least one equivalent of sodium hydroxide. The resultant product is water-insoluble and hence easily recoverable by the mere separation of resulting organic and aqueous layers.

The diallyl isocyanurate reactant may be prepared according to the method of US. Pat. No. 3,065,231 to Frazier and Sherman, Nov. 20, 1962, while the dimethyl sulfate may be any ,of those commercially available.

It is not known what the exact mechanism of the invention reaction is, but it is believed that the presence of the two allyl groups on the cyanuric acid nucleus may be activating the residual hydrogen so that reaction with dimethyl sulfate is possible.

The invention will be described further in conjunction with the following Specific examples, but it is to be understood that these are illustrative in nature and not intended to limit the invention thereto.

EXAMPLE 1 Diallyl isocyanurate (126 grams) was placed in a reaction flask equipped with stirrer, dropping funnel and reflux condenser. With reactants at ambient temperature, thirty grams of NaOH in 450 ml. of water was added to produce a clear solution of the sodium salt of diallyl isocyanurate. Dimethyl sulfate (81 grams) was added dropwise over a period of one hour. During the addition of the dimethyl sulfate, the temperature rose from 24 to 38 C. The reaction was completed by bringing the mixture to reflux for fifteen minutes. The mixture was extracted twice with 250-ml. portions of benzene. The resulting benzene solution was dried over sodium sulfate and evaporated to give 121 grams of crude diallyl methyl isocyanurate. Further purification was effected by distillation to give 97.6 grams of product, boiling point 149- 150/1.83.0 mm. Hg, n 1.5l271.5130. Yield of purified product was 72.8% of the theory.

Structure was established by the index of refraction and the infrared spectra of the product. Additional proof was obtained by reducing the compound with hydrogen over palladium catalyst at 25 60 C. to dipropyl monomethyl isocyanurate and determining the molecular weight (molecular weight calculated, 227; found 228).

EXAMPLE 2 A sample of the monomethyl diallyl isocyanurate prepared according to Example 1 was treated with 2 weight percent benzoyl peroxide, placed in a mold, and cast at 60 C. to form a hard, clear, resilient polymer. This polymer was found to have high resistance to chemical action. For example, it was highly resistant to acids. The polymer was somewhat more plastic than known polymers prepared from triallyl isocyanurate. It would therefore seem to be more suitable for use alone in molded or cast articles.

We claim:

1. A process for producing monomethyl diallyl isocyanurate which comprises reacting diallyl isocyanurate with dimethyl sulfate in an aqueous medium at a temperature 3 v between about 20 C. and 100 C. with dimethyl sulfate OTHER REFERENCES V being present in an amount between about 1 and 2 mols per mol of diauyl isocyqnuram I l ygljlitliigzts $1., J. Org. Chem. of the USSR, vol. 1, pp.

A Pmess accOrdmg clam 1 Wherem dlmethyl Chovnik et a1., Chem. Abstracts, vol. 62, col. 9155,

sulfate and dlallyl isocyanurate are present in about equl- 5 p 1965)- mlar amwnts' Frazier et al., J. Org. Chem, Vol. 25, pp. 1944-6 (1960).

3. A process according to claim 2 wherein said reaction o FMC Product Bulletin 10B, Cyanurrc Acid, FMC 15 carried out at a temperature of about 25 C., and at p New York p 1965).

least one equivalent of sodium hydroxide is present in 'd d' m. Sal me HENRY R. JILES, Primary Examiner R f C't d e erences l e I. M. FORD, Assistant Examiner UNITED STATES PATENTS 3,145,142 8/1964 Lansbury 260-248 XR US. Cl. X.R. 3,332,946 7/1967 Little 260248 15 260--77.5, 88.3

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 I522 I 253 Dated July 2J 1970 Inventor) Edwin D. Little, Jr. and Charles R. Walter, Jr.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 45 N should be N Column 1 line 55 N should be N CH CH SIGNED Mb QE'ALED mum EMU- mull. mum. Ja- 00m 1 arm IS m J 

